CN101652398A - Adhesive agent - Google Patents
Adhesive agent Download PDFInfo
- Publication number
- CN101652398A CN101652398A CN200780045934A CN200780045934A CN101652398A CN 101652398 A CN101652398 A CN 101652398A CN 200780045934 A CN200780045934 A CN 200780045934A CN 200780045934 A CN200780045934 A CN 200780045934A CN 101652398 A CN101652398 A CN 101652398A
- Authority
- CN
- China
- Prior art keywords
- preparation
- isocyanate
- component
- polymkeric substance
- potential reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 60
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 59
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 75
- 239000007787 solid Substances 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 29
- 125000001931 aliphatic group Chemical group 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000005056 polyisocyanate Substances 0.000 claims description 13
- 229920001228 polyisocyanate Polymers 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000013011 aqueous formulation Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 230000001464 adherent effect Effects 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 37
- 238000004132 cross linking Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- -1 cyclic aliphatic Chemical group 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 11
- 238000007725 thermal activation Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 210000003660 reticulum Anatomy 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 3
- 150000001463 antimony compounds Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002611 lead compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241001070947 Fagus Species 0.000 description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 206010023126 Jaundice Diseases 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920003009 polyurethane dispersion Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003911 antiadherent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000003339 best practice Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004835 fabric adhesive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000659 freezing mixture Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000020610 powder formula Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012173 sealing wax Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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Abstract
The present invention relates to adhesives based on aqueous dispersions and surface-deactivated isocyanate particles, and to latent-reactive coatings, films and powders prepared from such dispersions.
Description
The present invention relates to tackiness agent based on aqueous dispersion and the surface isocyanate particles of deactivating, and the potential reaction coating, film and the powder that make by this dispersion.
Has substrate linear, be particularly useful for thermal activation ground tack temperature sensitivity at the polyurethane dispersions polymkeric substance of the temperature crystalline polymer chain below 100 ℃.But add man-hour when 1 component, promptly not add under the linking agent situation, only reach low, with brilliant temperature of separating of this polymkeric substance or the relevant thermostability of softening temperature.In addition, to add the stability to hydrolysis in man-hour be not enough for a lot of application to 1 component.Owing to this reason, this aqueous dispersion polymerization thing uses usually under the hydrophilically modified liquid polyisocyanate situation together and processes.But, for the processing of two components, bring the character of improvement with higher technical costs.Must before the processing dispersion, directly prepare two component mixtures.In addition, the processing of two components is also producing deviation aspect isocyanate component that adds appropriate amount and the even stirring isocyanate component.
Look the difference of polymeric dispersions or isocyanate component type, the reactor lifetime of two component mixtures (Topfzeit) is 1-12 hour.In addition, the exsiccant binder layer must be processed in about 1-12h, because, otherwise the crosslinking reaction of proceeding owing to isocyanate groups no longer can be processed polymkeric substance under the adherent normal condition of thermal initiation.
Produce another shortcoming of this way thus: operation coating and curing, promptly applying adhesive-dispersion and thermal initiation is crosslinked, can not separate on time and space.The economic angle of not associating sees, on this time and the space separately for a lot of application be meet purpose and wish so.
Owing to this reason, in recent years the branch powder formula that contains solid-state tiny isocyanic ester has been strengthened work.The dispersing binder of this so-called potential reaction is by the dispersion and the solid isocyanate granulometric composition of the polymkeric substance of at least a isocyanate-reactive.In these years disclose the polymeric dispersions of aqueous formulation isocyanate-reactive, it contains the oligomeric solid isocyanate that comprises the uretdion groups that deactivates on tiny dispersive surface, with and as the purposes of coating and the agent of tackiness agent potential reaction cohesive.
The isocyanate particles of deactivating in the surface is meant such solid isocyanate, 0.1-25 wherein, and the isocyanate groups that always co-exists in isocyanate particles of preferred 0.5-8 equivalent percent reacts with deactivator.Deactivating especially of isocyanate particles can be by at EP-A 0 204 970, and US 4,595,445 and DE 10140206 in the deactivator described realize.
The isocyanate particles of deactivating in the surface is different with blocked isocyanate in principle.The preferred isocyanate groups that freely has the 92-99.5 equivalent percent of the isocyanate particles of deactivating in the surface.Otherwise isocyanate groups and end-capping reagents all in the blocked isocyanate react.For crosslinking reaction, the isocyanate groups of end capped isocyanic ester must for example go back and could discharge by the cracking of end-capping reagent.For the isocyanate particles of deactivating in the surface, needn't carry out the end capping that goes of isocyanate groups.
In EP-A 0204970, described a kind of by handle the method that polyisocyanates in liquid prepares the tiny polyisocyanates of stable dispersion with stablizer and higher shear power or grinding.Be suitable for this be those fusing points more than 10 ℃, preferred vulcabond and polyisocyanates more than 40 ℃.Described dispersion is used as linking agent.
EP A 1172390 discloses the isocyanic ester dispersion of shelf-stable, and its polymkeric substance by isocyanic ester that deactivates and isocyanate-reactive is formed, and they are back crosslinked under 5 ℃～40 ℃ temperature except that anhydrating.The dispersible preparation of this water-based shows good storage stability.
The shortcoming of the way of describing in these publications is that exsiccant coating, film or powder are not shelf-stables as far as possible.Drying by layer begins crosslinking reaction.Can not realize that with these work regulations procedure of processing coating/dry dispersion layer engages desirable room and time separately with being connected.
EP-A 1134245 has described the shelf-stable preparation that is formed by tiny vulcabond and polyisocyanates powder, and they need not the surface deactivate and just can directly process in the reactive polymeric dispersions of water-based isocyanate.For this prescription, cause crosslinking reaction by the temperature that the exsiccant layer is heated at least 65 ℃.
The shortcoming of the way of describing in the document is the following fact equally, can not be obtained coating, film or the powder of the potential reaction of shelf-stable by this prescription.Procedure of processing coating/dry dispersion layer be connected engage desirable room and time separately can not be with this work regulation realization.
The aqueous dispersion that EP-A 0922720 discloses the polymkeric substance that contains the polyisocyanates that deactivates at least a surface and at least a and isocyanate-reactive is used to prepare the layer at room temperature shelf-stable, potential reaction or the purposes of powder, and described layer or powder can be crosslinked by heating.
As polyisocyanates, can use the isocyanic ester of fusing point at all aliphatic series, cyclic aliphatic, heterocycle or aromatics more than 40 ℃.Stability and their speed of response when thermal initiation is crosslinked of pre-coating, film or powder can be subjected to the type of isocyanic ester, the amount of surface stabilizer, the solubility parameter of dispersed polymeres and the influence of catalyzer.
As catalyzer, mention typical catalysts for polyurethanes, as tin compound, iron cpd, lead compound, cobalt compound, bismuth compound, antimony compounds and zn cpds or its mixture, the alkyl thiol compound of dibutyl tin and tertiary amine.
Therefore, according to EP-A 0922720, the coating of the potential reaction of shelf-stable, film and powder are possible.Therefore, desirable tackiness agent coating and engaging process time and space are feasible in principle separately.
But, if the solid isocyanate that uses aromatics is as solid isocyanate, then depend on the effect of the long wave UV part in the sunlight, binder layer jaundice (KunststoffHandbuch 7,605-608 (1993)) can occur along with adhering junction is more and more aging
Can see that binder layer (adhesive tape that for example is used for paper/film connection of secret document) or binder layer are not wish this jaundice under not having fully by the connector situation of substrate covering (primer when for example making sports shoes).
Because the isocyanic ester of aliphatic series or do not absorb the shortwave UV part of sunlight based on the urethane of the isocyanic ester of aliphatic series, so this urethane is protected in principle in case turn to be yellow.Therefore, for the application of the powder of the film of the coating of the potential reaction of depending on non-variable color, potential reaction or potential reaction, the aliphatic solid isocyanate that uses the surface to deactivate is particularly advantageous.
But a shortcoming of aliphatic isocyanate is, compares with the isocyanate groups in conjunction with aromatics, and known its reactivity is littler.This puts for example by Ullmann ' s Encyclopedia of Industrial Chemistry, and the 6th edition, roll up 18,609 pages, Wiley-VCH Verlag, 2002, Isocyanantes, Organic is disclosed.Owing to this reason, can't use coating, film or powder so far based on the potential reaction of the aliphatic solid isocyanate that deactivates.Therefore, only be aromatics 1-methyl-2 from the free isocyanate groups group of the isocyanuric acid ester of isophorone diisocyanate (IPDI) to the relative reactivity of OH group, and the free isocyanate groups of 4-phenylene-vulcabond (TDI dimer) is rolled into a ball reactive about 1/50th of OH group.
According to coating, film or the powder of the potential reaction of EP-A 0922720, they contain the solid isocyanate of the aliphatic series of deactivating as the linking agent component, in order to make the crosslinked polymer of isocyanate-reactive, perhaps
A) need the at high temperature very long residence time, thereby crosslinking reaction proceeds to until the degree that reaches enough cross-linking density, perhaps
B) need a kind of catalyzer, the reaction between the polymkeric substance of this catalyzer acceleration aliphatic isocyanate group and isocyanate-reactive is even make crosslinking reaction also proceed to the cross-linking density of hope after short heat effect.
Do not having under the catalyzer situation, the crosslinking reaction in the layer of the potential reaction of this shelf-stable, film or the powder is carried out so slowly, to such an extent as to can not utilize this technology economically.Therefore, must keep at least 30 minutes down at 120 ℃ at the film of the potential reaction of using aliphatic IPDI tripolymer to make under as the solid isocyanate situation, thereby in adhering junction, reach sufficiently high cross-linking density.
The catalyzer of mentioning in EP A 0922720 (tin compound, iron cpd, lead compound, cobalt compound, bismuth compound, antimony compounds, zn cpds or its mixture, the alkyl thiol compound of dibutyl tin and tertiary amine) is the catalyzer that typically is used for isocyanate reaction.But, under the individual cases, this catalyzer also has shortcoming when it is used to prepare the powder of the film of coating, potential reaction of potential reaction or potential reaction, make and can not use them.
So organic Zn (IV) compound, DBTL for example, generally mix with dibutyl tin or tributyl tin, such as by " Assessment of the risk to health and environment posed the use oforganostannic Compounds (excluding use as biocide in antifouling paints) and adescription of the economic profile of the industry; Final report 19 July 2002, European Commission Health﹠amp; Consumer Protection Directorate-General " disclosed.Do not wish to use Zn (IV) compound by ecological angle yet.In addition, organic Zn (IV) compound is gone back the hydrolysis of the polyester segments of catalyst, polyester polyether polyols with reduced unsaturation chain, such as the dispersed polymeres of using it for the isocyanate-reactive in the potential reaction layer except the reaction of catalysis isocyanic ester.Owing to this reason, organic Zn (IV) compound can not be used for aliphatic solid isocyanate that catalytic surface deactivates and reaction based on the urethane dispersed polymeres of the crystal isocyanate-reactive of polyester polyol.
In addition, the catalyzer of prior art always has only the limited life-span usually in water-based system, that is, described catalyzer is because water effect hydrolysis fast more or less.This is applicable to the aqueous formulation of the dispersive polymer formation of the aliphatic solid isocyanate that deactivated by the surface and isocyanate-reactive; also be applicable to the coating of exsiccant potential reaction as far as possible, they also have the residual moisture that accounts for the about 0.6-10 weight of coating weight % water usually.Particularly this is applicable to and likes tin (IV) compound that uses in conventional system, as already mentioned DBTL or be applicable to bismuth carboxylate salt, for example 2 ethyl hexanoic acid bismuth (III) (K-Kat, King Industries, Norwalk, CT, USA), those as in WO 00/047642, also describing.
In order to be used for colourless binder layer, also can use the catalyzer that does not have color or variable color naturally.Therefore, the iron catalyst/cobalt catalyst mentioned in EP-A 0992720 or bismuth catalyst can not be used for the binder layer of non-variable color.
Therefore lead compound and antimony compounds should not use in principle because therefore its toxicity and environmentally harmful effect thereof are not favourable equally.
Another problem of reaction between the solid isocyanate that catalytic surface deactivates and the dispersed polymeres of isocyanate-reactive is the required ionic group of hydrophilization of dispersed polymeres polymer chain.Hydrophilization can realize by the carboxyl that is embedded on the polymer chain.This carboxyl may be by forming the catalytic activity that complex compound suppresses organo-tin compound.This is applicable to the Lewis acid of all high electric charges, for example titanium (IV) compound, zirconium (IV) compound.Generally the catalyzer that uses of the binding agent of aliphatic solid isocyanate, polyisocyanates and the hydrophilization that can deactivate with kinds of surface can not show with hydrophilization reagent and influence each other.
In EP-A 1599525, described and be used to make polyisocyanates and how pure and mild this polyurethane system that contains to quicken the solidified catalyzer.
According to this instruction operable (many) isocyanate component is any organic multiple isocyanate that has aliphatic series, cyclic aliphatic, araliphatic and/or aromatics bonded, free isocyanate groups, and they at room temperature are liquid or use solvent cut for this purpose.(many) isocyanate components are 10-15000mPas 23 ℃ viscosity.
The present invention is specifically related to be used for quicken polyisocyanates solidified catalyzer with polyvalent alcohol under the existence of aqueous solvent (so-called water-based two part polyurethanes lacquer, 2K-PUR sealing wax).The objective of the invention is, find acceleration, do not influence reactor lifetime in the case reacting between isocyanic ester and alcohol or the polyvalent alcohol in the presence of the water or quickening water-based 2K-PUR-system solidified catalyzer.This purpose is to realize that by the different salt of life cycle table the 5 and 6 (pair) family's element wherein the oxidation valency of each element at least+4.
Except metal catalyst, mention also that in EP-A 0992720 tertiary amine is as effective catalyzer.But described in EP A 0992720, tertiary amine is owing to absorbing carbon dioxide from air is lost its effect.For coating, film or the powder of potential reaction, this fact is undesirable especially, even also be not useable for the layer of potential reaction because the package stability of coating, film or powder is only considered rate of crosslinking.
Therefore the objective of the invention is, aqueous dispersion or dispersed mixture and the surperficial aliphatic solid isocyanate particle that deactivates and the preparation of catalyzer of the polymkeric substance of isocyanate-reactive are provided, can form colourless and coating, the film of potential reaction and the powder of potential reaction potential reaction colour stable, shelf-stable with it.Described catalyzer consider also should to be evaluated as aspect its toxicity positive.Crosslinking reaction in coating, film or the powder should reach the acceptable thermal activation time on industrial application.
This purpose realizes by the application's instruction: find surprisingly, the compound of the element of periodictable the 5th and 6 subgroups, wherein the oxidation valency of each element at least+4, reaction between the polymkeric substance of the solid isocyanate that deactivates of catalytic surface and isocyanate-reactive like this, make crosslinking reaction under temperature≤120 ℃, carry out, and in the longest 10 minutes basic to the greatest extent the end.In addition, the catalyzer of the application of the invention, the package stability of the coating of potential reaction, film/fibrous reticulum (Vliese) or powder was at least 3 months.
Therefore preparation of the present invention is following mixture of ingredients:
A) at least a aqueous dispersion or the dispersed mixture that has the polymkeric substance of the group of isocyanate-reactive
B) the tiny aliphatic solid polyisocyanates that deactivates in the surface that suspends in water at least basically
C) at least a compound of the element of periodictable the 5th and 6 subgroups, wherein the oxidation valency of each element be at least+4 and
D) optional other additive and auxiliary agent.
The aqueous formulation of potential reaction of the present invention can for example be coated on plane or the three-dimensional surface with spraying method, spread coating, spread coating or rolling method in any way.Obtain (in advance) coating of potential reaction after the drying.
Also can spraying method, spread coating, spread coating or rolling method be coated in interleaving paper (for example silicone paper or polyalkenes are provided with solid support materials such as anti-adherent paper) with it.Obtain film or fibrous reticulum from the load potential reaction after the drying, they are chosen wantonly after enclosing interleaving paper on the volume, can store when using as binder film.
By suitable commercial run, can obtain the solid of particle or powder type by preparation of the present invention.
Prescription for example of the present invention can discharge by the drying of spraying water.Obtain the powder of potential reaction like this, they are chosen wantonly can wear into small particle size by process of lapping subsequently.
The powder of potential reaction also can condense polymeric dispersions by the solid isocyanate particle that deactivates with the surface and obtain.In the case, the mixture that forms of the solid isocyanate that is deactivated by the polymeric dispersions of for example anionic property stabilization and surface is scattered in by rotor/stator-stirrer (for example Kotthoff company production) or by injection disperser and contains polyvalent cation (Ca for example
2+, Mg
2+, Al
3+) salts solution in.When the contact of anionic property group has the polymer beads surface of polyvalent cation, cause polymer beads to condense immediately, the solid isocyanate particle that this moment deactivates in the surface is wrapped in the concrement.Described concrement discharges water as far as possible by filter, centrifugal etc., and is dry under the temperature that is lower than the aliphatic solid isocyanate temperature of reaction of deactivating subsequently.Described concrement can for example be ground into the particle diameter of requirement optional after the drying in ball mill, ball mill, sand mill or injector-type mill in process of lapping.
The another kind of possibility of powder of preparation potential reaction is, under being lower than 0 ℃ temperature from aqueous formulation the freezing mixture that goes out the solid isocyanate that polymkeric substance and surface deactivates.Polymkeric substance/the isocyanate mixture of separating out discharges water outlet as far as possible by filter, centrifugal etc. subsequently, next carries out drying.The big grain powder that obtains then can be by suitably grinding, and optional this process of lapping must carry out at low temperatures, for example grinds to form the particle diameter of requirement in ball mill, ball mill, sand mill or injector-type mill.
The drying of the coating of potential reaction, film, fibrous reticulum or powder must be carried out under the temperature of the melt temperature of softening temperature that is lower than polymkeric substance or the aliphatic solid isocyanate that deactivates of surface or softening temperature.Adopt minimum softening temperature or melt temperature in the case.If exceed one of described temperature, then must cause crosslinked polymer.The coating of exsiccant potential reaction, film or powder still have the residual moisture of 0.1-5% as far as possible.
The aqueous dispersion that is used for preparation of the present invention preferably contains urethane or the polyurea dispersions with crystal soft polyester section as the dispersed polymeres of isocyanate-reactive.Especially preferably by the dispersion of the polyether polyols with reduced unsaturation of the isocyanate-reactive of crystalline polymer chain formation, they are measured by thermomechanical analysis under the temperature between 50 ℃ and 120 ℃ and separate crystalline substance (dekristallisieren) up to small part.
Solid isocyanate is all aliphatic series of softening temperature 〉=40 ℃ and vulcabond and polyisocyanates of cyclic aliphatic.Especially can use according to the present invention isophorone diisocyanate (
I, BayerMaterialScienceAG, Leverkusen), two-(4-isocyanate group cyclohexyl)-methane (
W, Bayer MaterialScience AG, Leverkusen), ω, ω '-diisocyanate based-1, the dimerization of 3-dimethyl cyclohexane (H6XDI) and trimerization product and these dimerisation products and trimerization mixture of products and by
I/
W, I/
H (
The H=hexamethylene diisocyanate)
W/
H, Desmodur W/H6XDI,
The mixing trimer that I/H6XDI forms.
Aliphatic solid isocyanate of the present invention must for example grind to form particle diameter d50＜100 μ m with suitable Ginding process before use in ball mill, ball mill, sand mill, disc refiner or injector-type mill, preferred d50＜10 μ m, preferred especially d50＜2 μ m.
The isocyanic ester that deactivates in the surface that suspends can be according to EP-A 0992720 and the preparation of EP-A 1172390 disclosed methods.
According to the present invention, as catalyzer, usually can life cycle table the 5 and the chemical compound of the element of 6 subgroups, wherein the oxidation valency of each element be at least+4.The preferred salt that uses these elements, wherein, these elements have described oxidation valency.Especially the elemental vanadium of prove out, niobium, tantalum, therefore the compound of molybdenum and tungsten preferably uses them.Elemental vanadium, tantalum, this compounds of molybdenum and tungsten for example is the salt of molybdic acid, as an alkali metal salt of molybdic acid and an alkali metal salt and the molybdic acid Si Yi Ji Phosphonium of vanadic acid, magnesium molybdate, calcium molybdate, zinc molybdate, lithium tungstate, potassium wolframate, wolframic acid, ammonium tungstate, phospho-wolframic acid, sodium columbate and tantalic acid sodium.An alkali metal salt of preferred especially vanadium and molybdenum.
Employed catalytic amount based on exsiccant (in advance) coating, exsiccant film or exsiccant powder meter, is 10-50000ppm, and in the case, addition manner is not depended in the effect of catalyzer.This means that catalyzer can
● add in the aqueous polymer dispersions
● in the preparation, add in the surperficial deactivation process of aliphatic solid isocyanate, or
● add in the prescription that the solid isocyanate that deactivated by polymeric dispersions, surface and optional other additive and auxiliary agent form.
Except effective catalysis, the catalyzer that the present invention uses also shows certain latency stage (the katalysis time-delay is used) when thermal activation.This (in advance) coating, film, fibrous reticulum or powder for potential reaction is favourable effect, makes catalyzer can not influence the package stability of layer, film, fibrous reticulum or the powder of potential reaction.
Figure among Fig. 1 by two kinds of binder films of research (
U 53 with
The progress of the inventory model of Z XP2589 (the IPDI tripolymer of micronization deactivates with 3mol% amino) in 120 ℃ of following thermal activation processs is come this phenomenon of exemplary expression.
For the binder film (being made comparing embodiment by dispersion 1) of the potential reaction that does not have catalyst, Inventory model is easy to direct rising when the beginning thermal activation. Adhesive with the potential reaction of lithium molybdate catalysis Film (being made embodiments of the invention by dispersion 3) does not at first show changing of inventory model under similarity condition Become. Just can see the catalytic effect of lithium molybdate after about 50 seconds. This moment, described inventory model was than there not being catalyst The binder film of potential reaction obviously raises quickly.
Pass through defeated at (in advance) of the potential reaction that is made by preparation of the present invention coating, film, fleece or powder Enter heat and cause cross-linking reaction. Pre-coating, film, fleece or powder must or be heated to polymer solution crystalline substance The temperature that temperature is above perhaps is heated to the softening temperature (melt temperature of the aliphatic solid isocyanate that deactivates Or glass transition temperature) above temperature.
Adhesive coating/joint method
(in advance) coating, binder film, adhesive fiber net or binder powders can apply, smear or be sprinkling upon On the surface of the substrate that engages (single face coating), perhaps apply, smear or be sprinkling upon the substrate that will engage On two surfaces (double-coated). In the case, best practice for every kind of applicable cases (single face or The wetability that has the substrate surface of the softening adhesive phase of thermoplasticity when double-coated) especially depending on thermal activation Can, and can in its routine work scope, be tried to achieve without difficulty by these those skilled in the art.
In principle, in order to form bonding connection, provide following methods:
1. short time layer of heat activated adhesive and cause cross-linking reaction:
The coating of potential reaction, the film of potential reaction, the fleece of potential reaction or potential reaction Powder by the short time thermal activation, for example in heat tunnel, by the IR radiation or by using microwave And be heated to the brilliant temperature of polymer solution or the above temperature of solid isocyanate softening temperature. Pressing then at once Under the power substrate surface is engaged. In the case, just begin cross-linking reaction by the short time thermal activation. Just reached afterwards the crosslinked final character of adhesive phase at 1-5 days.
The advantage of this way lower temperature when being processing step that engaging process is short and thermal activation. This Point is significant when wanting the substrate of tack temperature sensitivity especially.
2. Long Time Thermal activation, until reach the final character of bonding connection:
Fleece or the potential reaction of the coating of potential reaction, the film of potential reaction, potential reaction Powder wanting between the bonding substrate. Substrate is more than the brilliant temperature of polymer solution or aliphatic solid-isocyanic acid Be pressed the long period under the temperature more than the ester softening temperature. Can behind engaging process, reach in this way at once Final character to bonding connection.
The advantage of this way is can further process fast bonding connection or be and can engage Carry out quality testing after the journey at once.
3. combination short time thermal activation for example is used for fixing the activation of bonding part and Long Time Thermal with final crosslinked.
The advantage of this way is that substrate can be connected to each other in short engaging process. On room and time Realize final crosslinked in the second step that can separate with first engaging process.
Embodiment
Raw material
● the polymeric dispersions of isocyanate-reactive
● aliphatic solid isocyanate
● amine deactivates
● auxiliary agent:
NN 4501 (45%, in water) protective colloid; Manufacturer: BASF AG, 67056Ludwigshafen
Comparing embodiment (linking agent 1 and 2)
Introduce deionized water, emulsifying agent, the amine that deactivates, thickening material and solid isocyanate, under 2000rpm, in 15 minutes, be mixed into unit for uniform suspension with the dissolving plate.
The embodiment of the invention (linking agent 3-6)
Catalyzer at first is dissolved in the deionized water.Add emulsifying agent then, the amine that deactivates, thickening material and solid isocyanate, and with the dissolving plate under 2000rpm, in 15 minutes, be mixed into unit for uniform suspension.
For solid isocyanate is deactivated, linking agent 1 and 3 contains 3mol% amino, based on all available NCO group meters of IPDI tripolymer.Prescription 2,4,5 and 6 IPDI is trimerical to deactivate to use based on the available NCO group of IPDI tripolymer 7mol% amino and carries out.
Have the solid isocyanate particulate polymeric dispersions that deactivates on the surface:
Introduce polymeric dispersions.The prescription that under agitation adds the solid isocyanate that deactivates on the surface.
Dispersion 1 and 2 is the comparing embodiments that do not have catalyzer.Embodiment 3 to 6 is according to of the present invention.
Catalyst testing is to reactive effect of the pre-coating of potential reaction
The polymer dispersed body and function 200 μ m scrapers of embodiment 1-6 are coated in beech (Buchenholz) check body (check body size: 50mm * 140mm; 4mm is thick) area is on 50mm * 110mm, and 23 ℃ dry 1 hour down.After 3 hours, PVC film (supplier: Benecke company) under 80 ℃ and 100 ℃ (pressing temperature) and 4bar pressure, be attached on the binder layer through 5 minutes, 10 minutes, 15 minutes, 30 minutes and 60 minutes.From press, take out behind beech/PVC tape this connector is hung in the baking oven of 80 ℃ of constant temperature at once, and constant temperature 3 minutes.Respectively the 2.5kg weight is hung on the PVC film then, and the time that this adhering junction was loaded under 80 ℃ in stripping test (180 ° of angles) 5 minutes.
In order to prove crosslinking reaction, can consider the distance that in 5 minutes detection time, strips down.The distance transform that strips down is become mm/ minute.This value is more little, and the fast more or catalyzer of crosslinking reaction has activity more.
Estimate: it is crosslinked that catalyzer lithium molybdate, zinc molybdate and ortho-vanadic acid lithium cause quickening in the pre-coating of potential reaction.Dispersion 3-6 of the present invention is just crosslinked＜10 minutes (relatively dispersion 1 and 2=＞15 minute) backs in 30 minutes (relatively dispersion 1 and 2=＞60 minute) back and under 100 ℃ of press temperature under 80 ℃ of press temperature.
(note:, think that binder layer is crosslinked at value＜5mm/ minute; Mean: further measure nonsensical)
The effect of catalyzer in the binder powders of potential reaction
The powder of preparation potential reaction:
Dispersion 2 (comparison) and 4 (according to the present invention) stored 24 hours in low-temp. refrigerator under-5 ℃.Polymkeric substance is separated out with thick solid granulates form in the case.This prescription is heated to room temperature, and the polymkeric substance of being separated out separates with slurries by filtering.Make the polymkeric substance thorough drying subsequently, and to grind to form particle diameter be the about 100 μ m of d50 under cooling in injector-type mill.
Detect
The 2.4g powder evenly is sprinkling upon on cotton/polyester mixed goods of area 14cm * 24cm and (is equivalent to 70g/m approximately
2).This cotton/polyester mixed goods is pressed on the polyester textile that is forced into coating not under the gentle 1bar pressure at 80 ℃ in molding machine and is reached 2 minutes then.This adhering junction was stored 24 hours down at standard climate (23 ℃ of 50% relative humidity (r.h.)), next in creep rupture test, detect.
Creep rupture test
In order to carry out creep rupture test, the fabric adhesive tape at first hangs in the baking oven of 60 ℃ of constant temperature under not having load weight situation and constant temperature 30 minutes.Make this adhering junction (180 ° of stripping tests) load 50g weight subsequently, and under 60 ℃, placed again 30 minutes.After detecting in the past in 30 minutes, measure the distance [mm] that strips down.Next elevated the temperature in 30 minutes 10 ℃ at all respectively.Each thermograde back is in the past measured the distance that strips down.
At this, the powder of potential reaction and lithium molybdate quicken crosslinkedly can find out by the little peel distance of 150 ℃ of temperature at the most.There is not under the lithium molybdate situation adhering junction just separate fully down at 100 ℃ with powder.
Claims (21)
1, aqueous formulation, this aqueous formulation contains:
A) have the dispersed polymeres of isocyanate-reactive group
B) the aliphatic solid polyisocyanates that deactivates of the dispersive surface of at least a softening temperature 〉=40 ℃
C) one or more compounds of periodictable the 5th and 6 subgroup elements, wherein the oxidation valency of each element be at least+4,
D) optional other additive and auxiliary agent.
According to the preparation of claim 1, it is characterized in that 2, the polymkeric substance of described dispersive isocyanate-reactive contains carbamate groups and urea groups.
According to the preparation of claim 1, it is characterized in that 3, the polymkeric substance of described isocyanate-reactive contains the crystalline polymer unit.
According to the preparation of claim 1, it is characterized in that 4, the polymkeric substance of described isocyanate-reactive contains the softening section of crystalline polyester as the crystalline polymer unit.
5, according to the preparation of claim 1, it is characterized in that the particle diameter d50 of described aliphatic solid isocyanate＜100 μ m.
6, according to the preparation of claim 1, it is characterized in that the particle diameter d50 of described aliphatic solid isocyanate＜2 μ m.
According to the preparation of claim 1, it is characterized in that 7, described aliphatic solid isocyanate is the IPDI tripolymer.
According to the preparation of claim 1, it is characterized in that 8, at least a compound that uses molybdenum and vanadium is as component (c).
According to the preparation of claim 1, it is characterized in that 9, at least a compound that uses molybdenum is as component (c).
10, according to the preparation of claim 1, it is characterized in that, use lithium molybdate as component (c).
11, preparation is characterized in that according to the method for the preparation of claim 1-10, described component (c) is incorporated into the aqueous phase of dispersive polymkeric substance (a).
12, preparation is characterized in that according to the method for the preparation of claim 1-10 (c) is incorporated in the prescription of aliphatic solid isocyanate (b) with described component.
13, preparation is characterized in that according to the method for the preparation of claim 1-10, and described component (c) is incorporated in other additive and the auxiliary agent (d).
14, preparation is according to the method for the preparation of claim 1-10, it is characterized in that, described component (c) is incorporated into aliphatic solid isocyanate (b) and the additive of optional adding and the aqueous phase of the prescription that auxiliary agent is formed that deactivates by dispersive polymkeric substance (a), surface.
15, prepare the method for the potential reaction coating that forms by preparation, it is characterized in that, be coated on the substrate surface described preparation and drying according to claim 1-10.
16, the carrier-free potential reaction film or the fibroreticulate method that are formed by the preparation according to claim 1-10 of preparation is characterized in that, described preparation is coated on the interleaving paper, and drying is also taken off from interleaving paper.
17, the method for preparing the potential reaction powder that forms by preparation according to claim 1-10, it is characterized in that, the solids component of described prescription is separated out with known way own and is separated, perhaps obtain, and need next carry out littleization under the situation with own known by the described aqueous dispersion of drying.
18, according to the preparation of claim 1-10 purposes as tackiness agent.
19, the preparation according to claim 1-10 is used to prepare carrier-free film and fibroreticulate purposes.
20, be used to prepare the purposes of binder powders according to the preparation of claim 1-10.
21, by preparation adherent substrate according to claim 1-10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006058527.5 | 2006-12-12 | ||
| DE102006058527A DE102006058527A1 (en) | 2006-12-12 | 2006-12-12 | adhesives |
| PCT/EP2007/010345 WO2008071307A1 (en) | 2006-12-12 | 2007-11-29 | Adhesives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101652398A true CN101652398A (en) | 2010-02-17 |
| CN101652398B CN101652398B (en) | 2012-03-21 |
Family
ID=39226595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800459345A Active CN101652398B (en) | 2006-12-12 | 2007-11-29 | Adhesive agent |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20080171208A1 (en) |
| EP (1) | EP2099840B1 (en) |
| JP (2) | JP2010512436A (en) |
| KR (1) | KR101500768B1 (en) |
| CN (1) | CN101652398B (en) |
| AT (1) | ATE532807T1 (en) |
| BR (1) | BRPI0720278A2 (en) |
| DE (1) | DE102006058527A1 (en) |
| RU (1) | RU2466149C2 (en) |
| WO (1) | WO2008071307A1 (en) |
| ZA (1) | ZA200904058B (en) |
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| CN103328523A (en) * | 2011-01-05 | 2013-09-25 | 拜耳知识产权有限责任公司 | Aqueous 1K coating system and method for improving the appearance of grained wood surfaces |
| CN103653548A (en) * | 2012-09-18 | 2014-03-26 | 阿尔特科拉工业化学有限公司 | Technique for using powder binder during gluing of footwear component |
| CN104185664A (en) * | 2012-03-01 | 2014-12-03 | 德莎欧洲公司 | Use of latently reactive adhesive film for adhesive bonding of eloxated aluminium to plastic |
| CN105339442A (en) * | 2013-05-21 | 2016-02-17 | Ppg工业俄亥俄公司 | Coating composition |
| CN105694792A (en) * | 2014-12-15 | 2016-06-22 | H.B.富乐公司 | Reactive adhesive with enhanced adhesion to metallic surfaces |
| CN104918976B (en) * | 2013-07-30 | 2017-08-25 | H.B.富勒公司 | Polyurethane sticking film |
| CN112135853A (en) * | 2018-05-18 | 2020-12-25 | 汉高股份有限及两合公司 | Stable and low-curing-temperature 1K polyisocyanates |
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| EP2236533B1 (en) * | 2009-03-31 | 2011-11-09 | Sika Technology AG | Heat curing or heat activatable composition comprising a surface deactivated polyisocyanate |
| EP2244489A1 (en) | 2009-04-24 | 2010-10-27 | Bayer MaterialScience AG | Method for producing an electromechanical converter |
| DE202009015262U1 (en) | 2009-07-30 | 2010-03-11 | Lohmann Gmbh & Co. Kg | Latent reactive heat-activatable adhesive and adhesives made therewith |
| EP2284919A1 (en) | 2009-08-07 | 2011-02-16 | Bayer MaterialScience AG | Method for producing an electromechanical converter |
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| US10640702B2 (en) | 2013-08-01 | 2020-05-05 | Covestro Llc | Coated particles and methods for their manufacture and use |
| KR102354631B1 (en) * | 2014-02-26 | 2022-01-21 | 에이치. 비. 풀러, 컴퍼니 | Tacky, heat curable multi-layer adhesive films |
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| EP4153665A1 (en) | 2020-05-19 | 2023-03-29 | Covestro Deutschland AG | Method of manufacturing filled polyurethane particles |
| WO2021233750A1 (en) | 2020-05-19 | 2021-11-25 | Covestro Deutschland Ag | Method of manufacturing colorant-filled polyurethane particles |
| EP4296296A1 (en) | 2022-06-23 | 2023-12-27 | Covestro Deutschland AG | Method of manufacturing a particulate composition |
| WO2023247337A1 (en) | 2022-06-23 | 2023-12-28 | Covestro Deutschland Ag | Method of manufacturing a particulate composition |
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| DE3403499A1 (en) * | 1984-02-02 | 1985-08-08 | Bayer Ag, 5090 Leverkusen | USE OF HEAT-CURABLE POLYURETHANE RESIN REACTIVE ADHESIVES |
| DE3517333A1 (en) * | 1985-05-14 | 1986-11-20 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING STABLE DISPERSIONS OF FINE PARTICULATE POLYISOCYANATES AND THE USE THEREOF |
| US4788083A (en) * | 1986-03-27 | 1988-11-29 | Ashland Oil, Inc. | Tin or bismuth complex catalysts and trigger cure of coatings therewith |
| PT922720E (en) * | 1997-12-11 | 2002-01-30 | Bayer Ag | PROCESS FOR THE PREPARATION AND UTILIZATION OF LATENT LAYERS OR POSSIBLE REACTIVES STAYING THE STORAGE OF SURFACE-OFF SOLID POLYISOCYANATES AND DISPERSION POLYMERS WITH FUNCTIONAL GROUPS |
| DE10012826A1 (en) * | 2000-03-16 | 2001-09-20 | Bayer Ag | Adhesive preparations |
| KR100728462B1 (en) * | 2000-05-26 | 2007-06-13 | 아크조 노벨 엔.브이. | Photoactivatable coating composition |
| EP1164154A1 (en) * | 2000-06-15 | 2001-12-19 | Ag Bayer | Pressure-sensitive adhesives with improved shearing resistance at higher temperatures |
| DE10034637B4 (en) * | 2000-07-15 | 2004-04-08 | Jowat Ag | Storage stable isocyanate dispersions |
| EP1201695A1 (en) * | 2000-10-23 | 2002-05-02 | Huntsman International Llc | The use of polyisocyanate compositions as a binder for composite lignocellulosic materials |
| DE10140206A1 (en) * | 2001-08-16 | 2003-03-06 | Bayer Ag | One-component isocyanate-crosslinking two-phase systems |
| DE10248324A1 (en) * | 2002-10-17 | 2004-05-06 | Basf Coatings Ag | Coating material curable thermally and with actinic radiation and process for coating micropoporous surfaces |
| DE10308105A1 (en) * | 2003-02-26 | 2004-09-09 | Bayer Aktiengesellschaft | Polyurethane coating systems |
| DE10308104A1 (en) * | 2003-02-26 | 2004-09-09 | Bayer Ag | Polyurethane coating systems |
| DE10308106A1 (en) * | 2003-02-26 | 2004-09-09 | Bayer Aktiengesellschaft | New 2K PUR systems |
| DE102004026118A1 (en) * | 2004-05-28 | 2005-12-15 | Bayer Materialscience Ag | adhesives |
-
2006
- 2006-12-12 DE DE102006058527A patent/DE102006058527A1/en not_active Withdrawn
-
2007
- 2007-11-29 JP JP2009540625A patent/JP2010512436A/en active Pending
- 2007-11-29 AT AT07856300T patent/ATE532807T1/en active
- 2007-11-29 WO PCT/EP2007/010345 patent/WO2008071307A1/en active Application Filing
- 2007-11-29 EP EP20070856300 patent/EP2099840B1/en active Active
- 2007-11-29 BR BRPI0720278-4A2A patent/BRPI0720278A2/en not_active IP Right Cessation
- 2007-11-29 KR KR1020097014454A patent/KR101500768B1/en active IP Right Grant
- 2007-11-29 CN CN2007800459345A patent/CN101652398B/en active Active
- 2007-11-29 RU RU2009126425/04A patent/RU2466149C2/en not_active IP Right Cessation
- 2007-12-10 US US12/001,158 patent/US20080171208A1/en not_active Abandoned
-
2009
- 2009-06-10 ZA ZA200904058A patent/ZA200904058B/en unknown
-
2014
- 2014-08-21 JP JP2014168573A patent/JP5876548B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103328523A (en) * | 2011-01-05 | 2013-09-25 | 拜耳知识产权有限责任公司 | Aqueous 1K coating system and method for improving the appearance of grained wood surfaces |
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| CN104918976B (en) * | 2013-07-30 | 2017-08-25 | H.B.富勒公司 | Polyurethane sticking film |
| CN107603501A (en) * | 2013-07-30 | 2018-01-19 | H.B.富乐公司 | Polyurethane sticking film |
| CN107603501B (en) * | 2013-07-30 | 2021-05-28 | H.B.富乐公司 | Polyurethane adhesive film |
| CN105694792A (en) * | 2014-12-15 | 2016-06-22 | H.B.富乐公司 | Reactive adhesive with enhanced adhesion to metallic surfaces |
| CN105694793A (en) * | 2014-12-15 | 2016-06-22 | H.B.富乐公司 | Reactive adhesive capable of improving metal surface |
| CN112135853A (en) * | 2018-05-18 | 2020-12-25 | 汉高股份有限及两合公司 | Stable and low-curing-temperature 1K polyisocyanates |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2099840B1 (en) | 2011-11-09 |
| US20080171208A1 (en) | 2008-07-17 |
| ZA200904058B (en) | 2010-08-25 |
| JP2015004067A (en) | 2015-01-08 |
| JP5876548B2 (en) | 2016-03-02 |
| CN101652398B (en) | 2012-03-21 |
| DE102006058527A1 (en) | 2008-06-19 |
| RU2466149C2 (en) | 2012-11-10 |
| ATE532807T1 (en) | 2011-11-15 |
| JP2010512436A (en) | 2010-04-22 |
| KR20090088949A (en) | 2009-08-20 |
| WO2008071307A1 (en) | 2008-06-19 |
| KR101500768B1 (en) | 2015-03-09 |
| EP2099840A1 (en) | 2009-09-16 |
| BRPI0720278A2 (en) | 2014-01-28 |
| RU2009126425A (en) | 2011-01-20 |
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Effective date of registration: 20160603 Address after: German Monheim Patentee after: BAYER INTELLECTUAL PROPERTY GmbH Address before: Germany Leverkusen Patentee before: BAYER MATERIALSCIENCE AG Effective date of registration: 20160603 Address after: Leverkusen, Germany Patentee after: COVESTRO DEUTSCHLAND AG Address before: German Monheim Patentee before: BAYER INTELLECTUAL PROPERTY GmbH |